CN101045728A - Preparation method and use of compound with high insecticidal activity - Google Patents
Preparation method and use of compound with high insecticidal activity Download PDFInfo
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Abstract
This invention relates to a kind of nitryl methylene ramification, and its preparation method and application. Anthelminthic activity test indicate: this ramification has very high insecticidal activity to thorn-suck type, scrape-suck type gnathite pest, such as aphid, leafhopper, planthoppers, thrips, aleyrodids and resistant strain, also possess prevention and cure action to rice water weevil, acarid cochineal spider, hygiene pest and termite.
Description
Technical field
The present invention relates to the Nitromethylene analog derivative, its preparation method and application thereof.
Technical background
Nicotine (alkaloid of tobacco leaf extraction liquid) has unique mechanism of action very early as natural insecticide, and its target is postsynaptic nAChR (nAChRs), but it is to the high poison of people, and insecticidal activity is low.20th century, the mid-80 successfully developed first neonicotine sterilant-Provado by Bayer A.G.Develop a series of nicotinic insecticides such as thiophene worm quinoline, thiophene worm amine, thiophene worm piperazine, acetamiprid, Ti304, MTI-446 again in succession.Anabasine insecticide is because of the insecticidal activity height, and insecticidal spectrum is wide, and is low to Mammals and hydrocoles toxicity, and good system's rerum natura and suitable field stability are arranged, and become the important hot fields of agricultural chemicals initiative.
The Nitromethylene compounds is compared with Provado, have higher avidity and insecticidal activity, but its photo-labile and lower LogP value, limited of the application of this compounds as sterilant, people such as Li Zhong carry out structure of modification to highly active Nitromethylene compounds, on the basis of existing Nitromethylene compounds, increase the structure of ring and control the spatial orientation of nitro, successfully found a series of high-activity compounds, make it be applied to sterilant.These compounds are disclosed in Chinese patent application number 200410084457.1 (publication number CN1631887).Yet comparatively complicated in the preferred compound technology of above-mentioned patent application, cost is comparatively expensive, has therefore limited these application of compound.
Therefore, this area presses for the high compound of exploitation insecticidal activity, and the method for making of described compound is easy, with low cost.
Summary of the invention
The object of the invention just provides a class insecticidal activity height, method for making nitromethylene derivatives easy, with low cost, its preparation technology and uses thereof.
A first aspect of the present invention provides the nitromethylene derivatives with following structural formula I:
In the formula:
R
1Or/and five yuan of sulphur or hexa-member heterocycle base, or halogenated nitrogenous, oxygen is or/and five yuan of sulphur or hexa-member heterocycle base for nitrogenous, oxygen;
R
2Be H, C
1～C
4Alkyl, C
1～C
4Alkoxyl group or aryl; R
3Be H, C
1～C
4Alkyl or C
1～C
4Alkoxyl group; R
4Be H, C
1～C
4Alkyl, C
1～C
4Alkoxyl group or aryl;
R
5Be H, C
1～C
8Saturated or unsaturated alkyl, halogenated C
1～C
8Saturated or unsaturated alkyl ,-CH
2CH
2OCH
2CH
3,-CH
2CH
2OCH
3, C
1～C
8Saturated or unsaturated-oxyl;
Preferred R
1Be pyridyl, thiazolyl, pyrimidyl, tetrahydrofuran base He a kind of or its chloro thing in the oxazolyl; R
5Be H or C
1～C
5Saturated or unsaturated alkyl, the C in fluorine or chlorine generation
1～C
5Saturated or unsaturated alkyl ,-CH
2CH
2OCH
2CH
3Or-CH
2CH
2OCH
3, C
1～C
8Saturated or unsaturated alkoxyl group.Preferred R
1For
Preferred R
5Be H or C
1～C
5Saturated or unsaturated alkyl.
Preferred R
2Be H, C
1～C
3Alkyl or C
1～C
3Alkoxyl group.
Preferred R
3Be H, C
1～C
3Alkyl or C
1～C
3Alkoxyl group.
Preferred R
4Be H, C
1～C
3Alkyl or C
1～C
3Alkoxyl group.
Preferably, described aryl is the phenyl of replacement or non-replacement, and described substituting group is selected from C
1-C
3Alkyl, C
1-C
3Alkoxyl group, halogen ,-NH
2, NO
2, or-OH.
It (is R that the particularly preferred compound of one class has structure shown in the following formula A
3=R
5=H):
R in the formula
2, R
4As above definition.
Preferred R
1For
Preferred R
2Be methyl;
Preferred R
4Be H or C
1～C
3Alkyl or C
1～C
3Alkoxyl group.
A second aspect of the present invention provides a kind of pesticide composition, and formula I derivative of the present invention or its agricultural that it contains 0.0001wt%-99.9wt% go up suitable salt, and agricultural goes up acceptable diluent or carrier.
In another preference, the concentration that described formula I derivative or its agricultural go up acceptable salt is 10-500ppm, preferably 20-100ppm.
In another preference, the formulation of described pesticide composition is various conventional pesticide formulations, as bait formulation etc.
A third aspect of the present invention, a kind of method of pest control is provided, plant seed of using at needs or plant leaf and/or fruit or plant are growing or are expecting the place that will grow, use the formula I derivative of the present invention of insecticidal effective dose (as 10-500ppm, more preferably 20-100ppm).
In another preference, described insect is selected from: pierce-suck type, scratching mouthparts insect, rice water weevil, acarid red spider, sanitary insect pest (as blattaria, acarian, flea, ant) and termite.
A fourth aspect of the present invention provides the purposes of formula I derivative of the present invention, is used to prepare agricultural chemical insecticide.
A fifth aspect of the present invention provides a kind of method for preparing formula I derivative of the present invention, and described method comprises step:
(a) in appropriate solvent, formula II compound and formula III compound are reacted in 60-100 ℃, form formula IV compound;
In the formula, Z=Cl ,-OR ' ,-SR ', wherein R '=C1-C3 alkyl (R '=CH3) preferably;
(b) in appropriate solvent, with formula IV compound and formula V compound under the acid catalysis condition in 0-90 ℃ of reaction, form formula (VI) compound:
(c) in appropriate solvent, with formula VI compound and formula VII under the effect of the acid of catalytic amount in 30-70 ℃ of reaction, form formula I compound,
R
5OH (VII)
Wherein, described in the definition such as claim 1 of R1, R2, R3, R4 and R5;
Supplementary condition are, when Z be-OR ' or-SR ' time, any two steps among step (a) and (b), (c) or three steps can merge carries out.
Embodiment
The inventor increases the structure of ring, thereby both can strengthen the stability of compound to light through extensive and deep research on the basis of existing Nitromethylene compounds, can strengthen the fat-soluble of its again.In addition, the present invention is the substituting group by being connected with ehter bond also, the spatial orientation of control nitro and fat-soluble.In addition, by screening, preferred insecticidal activity height of a class and the easy formula I derivative of preparation technology have been selected to a large amount of compounds.Finished the present invention on this basis.
Particularly, the inventor provides three concrete operational paths, in these selection process, reduce temperature, changed solvent, thereby simplified operational path greatly, reduce the preparation cost of compound, made the actual application value of compound be improved.
In addition, to the desinsection test shows of formula I compound, formula I derivative is a kind of insecticidal active compound of wide spectrum.Nitromethylene analog derivative of the present invention is not only to pierce-suck type, scratching mouthparts insect, as aphid, leafhopper, plant hopper, thrips, aleyrodid and resistant strain thereof very high insecticidal activity is arranged, also efficient to rice water weevil, acarid such as red spider, also can be used for the control of sanitary insect pest, termite etc.
The preparation method
Nitromethylene derivatives of the present invention can be synthetic by following reactions steps:
Route one
Route two
Route three
Route one:
(1) Nitromethane 99Min., dithiocarbonic anhydride are placed there-necked flask, with alcohol as solvent.At room temperature, be added drop-wise to the alcoholic solution of potassium hydroxide lentamente.Temperature is to be controlled between 0～35 ℃ reaction 2-10 hour.Filter out solid, obtaining crude product is pale brown toner powder solid 2-nitro-ethene-1, and 1-connects curing potassium.
(2) with 2-nitro-ethene-1,1-connects curing potassium with after the alcohol dissolving, drips methyl-sulfate solution, stirs under the room temperature 2-8 hour.Solid is separated out in filtration, obtains crude product light brown yellow pulverulent solids 1,1-two thiomethyls-2-nitroethylene.
(3) acetonitrile solution of 2-chloro-5-chloromethylpyridine is added drop-wise in two amine aqueous solutions of 5-10 times of molar weight, between 0-50 ℃, reacts 5-10 hour.Add water, chloroform extraction is spin-dried for solvent, is spin-dried for diamines as far as possible, obtains product N
*1
*-(6-chloro-3-picolyl)-diamines.
(4) N
*1
*-(6-chloro-3-picolyl)-diamines and 1,1-two thiomethyls-2-nitroethylene are made solvent with ethanol, backflow 4-8 hour, get product Nitromethylene compounds.
(5) Nitromethylene compounds and olefine aldehydr obtain having the new Nitromethylene compounds of hydroxyl under acid (hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid etc.) catalytic condition.
(6) have the new Nitromethylene compounds of hydroxyl and the various alcohol of about quintuple, make solvent with methylene dichloride, under the hydrochloric acid effect of catalytic amount, refluxing obtains containing Nitromethylene structure ether derivative.This method can improve yield 30-50%, reduces side reaction.
New Nitromethylene compounds and various acyl chlorides or acid anhydrides with hydroxyl under acid binding agent (organic and mineral alkali such as pyridine, triethylamine or salt of wormwood, potassium hydroxide etc.) effect, obtain target compound.
Route two:
(1) nitrate mixture with 36% hydrochloric acid and 65% adds in the there-necked flask, drips vinylidene chloride, the extraction that adds methylene chloride then, and the oil reservoir washing adds alkali, and after reaction was finished, oil reservoir was washed in the extraction that adds methylene chloride, and dry filter obtains yellow liquid.
(2) 3,4,5,6 steps, this method can improve yield 20-40% with route one.
Route three: (one kettle way)
1,2,3 steps are with route one, below several steps adopt one kettle ways:
N
*1
*-(6-chloro-3-picolyl)-diamines and 1,1-two thiomethyls-2-nitroethylene, make solvent with corresponding alcohol, add olefine aldehydr and acid (hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid etc.) after backflow 4-8 hour, backflow obtains the pairing ether derivative that contains the Nitromethylene structure of various alcohol, this method has reduced by a step separates, and can improve yield 20-40%.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise per-cent and umber calculate by weight.
Embodiment 1
1-(6-chloro-3-picolyl)-7-methyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazos [1,2-a] pyridine-5-alcohol (compound 1) synthetic:
(1) 2-nitro-ethene-1,1-connects the synthetic of curing potassium
With the Nitromethane 99Min. of 4.0g (0.03mol), the there-necked flask that 6ml (0.05mol) dithiocarbonic anhydride places 100ml, the ethanol that adds 10ml begins to stir as solvent.The potassium hydroxide that takes by weighing 8g (0.14mol) at room temperature, is added drop-wise to (about 30min) in the above-mentioned solution lentamente with behind the dissolve with ethanol of 40ml.Because temperature of reaction is at that time depended in reaction process heat release, rate of addition, temperature is advisable to be controlled between 30～35 ℃.After dropwising, allow reaction continue to stir 2 hours.Filter out solid at last, obtaining crude product is pale brown toner powder solid, productive rate 72%.
Synthesizing of (2) 1,1-two thiomethyls-2-nitroethylene
Add 2-nitro-ethene-1 of 2g (0.0094mol) in round-bottomed flask, 1-connects curing potassium, with the dry CH that crosses of 10ml
3OH dissolves it.0.0187mol Me
2SO
4Be added drop-wise in the above-mentioned solution, stirred 2 hours under the room temperature, filter the solid of separating out, obtain crude product light brown yellow pulverulent solids, productive rate is 70%.GC/MS(m/s)165(31)M
+，148(17)，104(66)，86(100)，72(93)，57(20)。
(3) N
*1
*Synthesizing of-(6-chloro-3-picolyl)-1
The quadrol of the salt of wormwood of 4.2g (0.03mol), 10ml (0.15mol) is added in the flask of 50ml, take by weighing in addition 4.8g (0.03mol) to chloropyridine, it is dissolved in the acetonitrile of 15ml, in ice bath, slowly drip while stirring (about 20min).After dropwising, remove ice bath, allow reaction continue to stir 8 hours under the normal temperature.Behind the stopped reaction, add a large amount of water with salt of wormwood and quadrol dissolving, use dichloromethane extraction, collect lower floor's organic phase, dry, be spin-dried for solvent and (spin off the quadrol in the solvent as far as possible, because the existence of quadrol can influence next step reaction), obtaining product is yellow oily liquid, productive rate about 68%.GC?MS(m/s)185(5)M
+，155(49)，126(100)，99(9)，90(12)。
(4) 2-chloro-5-(2-Nitromethylene-1-imidazolyl methyl)-pyridine is synthetic
2.5g (0.0178mol) 1, the N of 1-two thiomethyls-2-nitroethylene, 3.3g (0.0178mol)
*1
*-(6-chloro-3-picolyl)-1, the ethanol of adding 15ml refluxed 4 hours under 80 ℃～90 ℃ condition.Cooling, solid to be separated out concentrates, filtration, drying obtain pale yellow powder shape solid, and productive rate is 56%; R
f=0.46 (sherwood oil: ethyl acetate=1: 1); Mp=156.9 ℃～161.8 ℃.GC?MS(m/s)220(25)，126(100)，90(9)。
(5) 1-(6-chloro-3-picolyl)-7-methyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazos [1,2-a] pyridine-5-alcohol (compound 1) synthetic, reaction equation is as follows:
2-chloro-5-(2-Nitromethylene-imidazolidine-1-ylmethyl)-pyridine with 10.16g (0.04mol), the 100ml anhydrous acetonitrile, the crotonic aldehyde of about 5ml, the AcOH of about 4ml catalytic amount (can suitably add) places the round-bottomed flask of 250ml, 40-45 ℃ of stirring, there is a large amount of solids to separate out after about one day, stops heating, cooling, filtration obtains thick product, it is pale yellow powder shape solid that recrystallization (MeCN makes solvent) obtains pure product, and productive rate is 67%, mp=175.6～177.1 ℃.
1H NMR (500MHz, DMSO): 8.32 (d, J=2.14Hz, 1H, pyridine-H), 7.78 (dd, J
1=2.37Hz, J
2=8.21Hz, 1H, pyridine-H), 7.48 (d, J=8.22Hz, 1H, pyridine-H), 4.80 (m, 1H ,-CHOH), 4.64 (dd, J
1=J
2=15Hz, 2H ,-CH
2-N-), 3.64 (m, 4H, imidazolidine-H), 1.91 (m, 2H ,-CH
2CH-), 1.71 (m, 1H ,-CHCH
2-), 1.01 (d, 3H ,-CH
3); HR-MS (EI, 1.08e3): M
+.Be C
14H
17N
4O
3Cl, calculated value: 324.0989, measured value: 324.0986, m/z (%)=324 (0.75), 306 (4), and 294 (10), 291 (100), 244 (33), 126 (72)
Ultimate analysis
C％ H％ N％
Theoretical value 51.78 5.28 17.25
Measured value 51.56 5.17 17.09
Embodiment 2
1-(6-chloro-3-picolyl)-5-methoxyl group-7-methyl-8 nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-] pyridines (compound 2) synthetic
Synthesizing of (1) 1,1-two chloro-2-nitroethylenes
In the there-necked flask of stirring is housed, the mixture of the hydrochloric acid 20.85g (0.2055mol) of adding 36% and 65% nitric acid 19.9g (0.2055mol).Drip vinylidene chloride 15.5g (0.1575mol), control dropping temperature between 20～25 ℃, insulated and stirred 3 hours.Add the 50ml dichloromethane extraction, washing is between the about 3-4 of control oil reservoir pH.5-6 is restrained alkali join in the 120ml water and dissolve, be cooled to 0 ℃, add oil reservoir gradually, keep 0 ℃ of temperature.Violent stirring 5 minutes again behind reinforced the finishing.Dichloromethane extraction, layering, the oil reservoir washing, dry filter obtains the about 13.5-17.5 gram of yellow liquid.
(2) N
*1
*Synthesizing of-(6-chloro-3-picolyl)-1
With step (3) among the embodiment 1.
(3) 2-chloro-5-(2-Nitromethylene-1-imidazolyl methyl)-pyridine is synthetic
2.53g (0.0178mol) 1, the N of 1-two chloro-2-nitroethylenes, 3.3g (0.0178mol)
*1
*-(6-chloro-3-picolyl)-1, the ethanol of adding 15ml refluxed 4 hours under 80 ℃～90 ℃ condition.Cooling, solid to be separated out concentrates, filtration, drying obtain pale yellow powder shape solid, and productive rate is 56%; R
f=0.46 (sherwood oil: ethyl acetate=1: 1); Mp=156.9 ℃～161.8 ℃.GC?MS(m/s)220(25)，126(100)，90(9)。
(4) 1-(6-chloro-3-picolyl)-5-methoxyl group-7-methyl-8 nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-] pyridines (compound 2) synthetic
The compound 1 of 0.324g (0.001mol) is joined in the there-necked flask of 50ml, add the methyl alcohol of 15ml and the Glacial acetic acid of catalytic amount again, reflux, TLC follows the tracks of reaction.After question response finishes, remove and desolvate, column chromatography for separation obtains the pure product of yellow powder shape, and productive rate is 60%.Mp=164.0～165.4 ℃;
1H NMR (500MHz, CDCl
3): 8.32 (d, J=2Hz, 1H, pyridine-H), 7.86 (dd, J
1=2.4Hz, J
2=8.22Hz, 1H, pyridine-H), 7.32 (d, J=8Hz, 1H, pyridine-H), 4.78 (dd, J
1=15Hz, J
2=15Hz, 2H ,-CH
2-N-), 4.5 (t, J
1=3Hz, J
2=3Hz, 1H ,-CHO-), 3.65 (m, 4H, imidazolidine-H), 3.36 (m, 3H ,-OCH
3), 1.87 (m, 2H ,-CH
2CH-), 1.76 (m, 1H ,-CHCH
2-); 1.23 (d, 3H ,-CH
3); HR-MS (EI, 2.31e4): M
+.Be C
15H
19N
4O
3Cl, calculated value: 338.1146, measured value: 338.1150, m/z (%) 338 (1), 308 (9), and 306 (1), 291 (100), 244 (22), 126 (38)
Ultimate analysis
C％ H％ N％
Theoretical value 53.18 5.65 16.54
Measured value 53.35 5.43 17.34
Embodiment 3
1-(6-chloro-3-picolyl)-5-oxyethyl group-7-methyl-8 nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-] pyridines (compound 3) synthetic, reaction equation is as follows:
2-chloro-5-(2-Nitromethylene-imidazolidine-1-ylmethyl)-pyridine with 10.16g (0.04mol), the 100ml dehydrated alcohol, the crotonic aldehyde of about 5ml, the AcOH of catalytic amount places the round-bottomed flask of 250ml, reflux, TLC follows the tracks of reaction, after reaction finishes, removes and desolvates, column chromatography for separation obtains the pure product of yellow powder shape, it is yellow powder shape solid that column chromatography for separation obtains pure product, and productive rate is 75%, mp=138.8～140.3 ℃.
1H NMR (500MHz, CDCl
3): 8.31 (d, J=2Hz, 1H, pyridine-H), 7.87 (dd, J
1=2Hz, J
2=8Hz, 1H, pyridine-H), 7.33 (d, J=8Hz, 1H, pyridine-H), 4.76 (dd, J
1=15Hz, J
2=15Hz, 2H ,-CH
2-N-), 4.56 (t, J
1=3Hz, J
2=3Hz, 1H ,-CHO-), 3.60 (m, 4H, imidazolidine-H), 3.57 (m, 2H ,-O-CH
2-), 3.53 (m, 1H ,-CHCH
2-), 2.01 (m, 2H ,-CH
2CH-), 133 (t, J
1=7Hz, J
2=7Hz, 3H ,-CHCH
3), 1.24 (d, 3H ,-CH
3); HR-MS (EI, 7.04e3): M
+.Be C
16H
21N
4O
3Cl, calculated value: 352.1302, measured value: 352.1306, m/z (%)=352 (3), 337 (7), and 306 (8), 291 (100), 244 (30), 126 (42)
Ultimate analysis
C％ H％ N％
Theoretical value 54.47 6.00 15.88
Measured value 54.64 5.96 15.64
Embodiment 4
1-(6-chloro-3-picolyl)-5-propoxy--7-methyl-8 nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-] pyridines (compound 5) synthetic, reaction equation is as follows:
With 1-(6-chloro-3-picolyl)-8-nitro-7-methyl isophthalic acid of 0.972g (0.03mol), 2,3,5,6,7-six hydrogen imidazos [1,2-a] pyridine-5-alcohol, about 6g n-propyl alcohol (about 5 times 1-(6-chloro-3-picolyl)-8-nitro-7-methyl isophthalic acid, 2,3,5,6, the amount of 7-six hydrogen imidazos [1,2-a] pyridine-5-alcohol), the 70ml methylene dichloride joins in the there-necked flask of 100ml, add 3-4 and drip hydrochloric acid, reflux, TLC follows the tracks of reaction, reacts about 8 hours, column chromatography for separation, use earlier sherwood oil: ethyl acetate=5: 1 wash-outs, n-propyl alcohol is gone out, use methylene dichloride then: ethanol=10: 1 wash-outs, obtain yellow solid, productive rate is 72%.Mp=130.2～131.9 ℃;
1H NMR (500MHz, CDCl
3): 8.36 (d, J=2Hz, 1H, pyridine-H), 7.79 (dd, J
1=2Hz, J
2=8Hz, 1H, pyridine-H), 7.48 (d, J=8Hz, 1H, pyridine-H), 4.81 (d, J
1=15Hz, J
2=15Hz, 2H ,-CH
2-N-), 4.54 (t, J
1=3Hz, J
2=3Hz, 1H ,-CHO-), 3.77 (m, 2H ,-O-CH
2-), 3.66 (m, 4H, imidazolidine-H), 2.81 (m, 2H ,-CH
2CH-), 1.92 (m, 1H ,-CHCH
2-), 1.65 (m, 2H ,-CH
2CH
3), 1.23 (t, J
1=7Hz, J
2=7Hz, 3H ,-CHCH
3), 1.03 (d, 3H ,-CH
3).HR-MS (EI, 6.83e3): M
+.Be C
17H
23N
4O
3Cl, calculated value: 366.1459, measured value: 366.1487, m/z (%)=366 (3), 351 (8), and 306 (4), 291 (100), 244 (30), 126 (46)
Ultimate analysis
C％ H％ N％
Theoretical value 55.66 6.32 15.27
Measured value 55.50 6.21 15.08
Embodiment 5
1-(6-chloro-3-picolyl)-5-butoxy-7-methyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazos [1,2-a] pyridines (compound 7) synthetic, reaction equation is as follows:
3.713g (0.02mol) 1, the N of 1-two thiomethyls-2-nitroethylene, 3.305g (0.02mol)
*1
*-(6-chloro-3-picolyl)-1, the propyl carbinol of adding 15ml, under 80 ℃～90 ℃ condition, refluxed 4 hours, in reaction solution, add 3ml crotonic aldehyde, reflux then, TLC follows the tracks of reaction, and column chromatography for separation obtains yellow solid, and productive rate is 75%.Mp=103.5～105.2 ℃;
1HNMR (500MHz, CDCl
3): 8.32 (d, J=2Hz, 1H, pyridine-H), 7.85 (dd, J
1=2Hz, J
2=8Hz, 1H, pyridine-H), 7.33 (d, J=8Hz, 1H, pyridine-H), 4.74 (d, J
1=15Hz, J
2=15Hz, 2H ,-CH
2-N-), 4.49 (t, J
1=3Hz, J
2=3Hz, 1H ,-CHO-), 3.77 (m, 2H ,-O-CH
2-), 3.57 (m, 4H, imidazolidine-H), 2.86 (m, 2H ,-CH
2CH
2CH
2CH
3), 2.81 (m, 2H ,-CH
2CH-), 1.92 (m, 1H ,-CHCH
2-), 1.63 (m, 2H ,-CH
2CH
2CH
3), 1.35 (m, 4H ,-CH
2CH
3), 1.27 (t, J
1=7Hz, J
2=7Hz, 3H ,-CHCH
3), 0.92 (d, 3H ,-CH
3).HR-MS (EI, 6.83e3): M
+.Be C
17H
23N
4O
3Cl, calculated value: 366.1459, measured value: 366.1487, m/z (%)=366 (3), 351 (8), and 306 (4), 291 (100), 244 (30), 126 (46)
Ultimate analysis
C％ H％ N％
Theoretical value 56.76 6.62 14.71
Measured value 56.68 6.41 14.52
Embodiment 6
1-(6-chloro-3-picolyl)-7-methyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazos [1,2-a] pyridine-5-yl acetate (compound 11) synthetic, reaction equation is as follows:
0.001mol compound 1 join in the round-bottomed flask of 50ml, add aceticanhydride and the 0.001mol pyridine of 0.001mol, stirring at room, TLC follows the tracks of reaction.After question response finishes, remove and desolvate, column chromatography for separation obtains yolk yellow powdered pure product, and productive rate is 70%.Mp=144～145.7 ℃; IR (KBr cm
-1) 2903,2370,1713,1332,1203,1123,1071,1000,973,830,592; δ (ppm) 500MHz:8.33 (d, J=2Hz, 1H, pyridine-H), 7.88 (dd, J
1=2Hz, J
2=8Hz, 1H, pyridine-H), 7.36 (d, J=8Hz, 1H, pyridine-H), 4.79 (d, J
1=15Hz, J
2=15Hz, 2H ,-CH
2-N-), 4.48 (t, J
1=3Hz, J
2=3Hz, 1H ,-CHO-), 4.12 (m, 3H ,-OCOCH
3), 3.62 (m, 4H, imidazolidine-H), 2.97 (m, 2H ,-CH
2CH
2-), 1.87 (m, 2H ,-CH
2CH-), 1.76 (m, 1H ,-CHCH
2-); HR-MS (EI, 2.08e3): M
+.Be C
15H
19N
4O
4Cl, calculated value: 366.1095, measured value: 366.1093, m/z (%)=366 (1), 351 (11), and 336 (8), 306 (19), 291 (100), 244 (22), 126 (38)
Ultimate analysis
C％ H％ N％
Theoretical value 52.39 5.22 15.27
Measured value 52.23 4.98 15.02
Embodiment 7
1-(5-chloro-2-methylthiazol base)-7-methyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazos [1,2-a] pyridine-5-alcohol (compound 12) synthetic:
(1): N
*1
*Synthesizing of-(5-chloro-2-methylthiazol base)-1:
The salt of wormwood of 0.03mol, the quadrol of 10ml (0.15mol) are added in the flask of 50ml, take by weighing 0.03mol 2-chloro-5-5-chloromethyl thiazole in addition, it is dissolved in the acetonitrile of 15ml, in ice bath, slowly drip while stirring.After dropwising, remove ice bath, allow reaction continue to stir 8 hours under the normal temperature.Behind the stopped reaction, add a large amount of water with the dissolving of salt of wormwood and quadrol, use dichloromethane extraction, collect lower floor's organic phase, drying, be spin-dried for solvent, obtaining product is yellow oily liquid, productive rate about 70%.GC?MS(m/s)191(21)M
+，132(100)。
(2) 1-((2-diuril azoles-5-yl) methyl)-2-(Nitromethylene)-1-tetrahydroglyoxaline is synthetic:
2.5g (0.0178mol) 1, the N of 1-two thiomethyls-2-nitroethylene, 3.3g (0.0178mol)
*1
*-(6-chloro-3-picolyl)-1, the ethanol of adding 15ml refluxed 4 hours under 80 ℃～90 ℃ condition.Cooling, solid to be separated out concentrates, filtration, drying obtain pale yellow powder shape solid, and productive rate is 56%; GC/MS (m/s) 226 (24), 132 (100), and 77 (9).
(3) 1-(5-chloro-2-methylthiazol base)-7-methyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazos [1,2-a] pyridine-5-alcohol is synthetic, and reaction equation is as follows:
With 1-((2-diuril azoles-5-yl) methyl)-2-(Nitromethylene)-1-tetrahydroglyoxaline of 0.002mol, the anhydrous acetonitrile of 15ml, the crotonic aldehyde of 0.25ml, the acetate of catalytic amount place the end flask of 50ml.40-45 ℃ of stirring has a large amount of solids to separate out after about one day, stops heating, and cooling is filtered and to be obtained thick product, and it is pale yellow powder shape solid that recrystallization (MeCN makes solvent) obtains pure product, and productive rate is about 40%, mp=172～174.6 ℃.IR (KBr, cm
-1) 3194,1564,1545,1373,1310,1150;
1H NMR (500MHz, DMSO): 7.38 (s, 1H, thiazole-H), 4.83 (m, 1H ,-CHOH), 4.59 (dd, J
1=J
2=15Hz, 2H ,-CH
2-N-), 3.56 (m, 4H, imidazolidine-H), 1.93 (m, 2H ,-CH
2CH-), 1.75 (m, 1H ,-CHCH
2-), 1.13 (d, 3H ,-CH
3); HR-MS (EI, 3.38e3): M+. is C12H15N4O3ClS, calculated value: 330.0553, measured value: 330.0786, m/z (%)=330 (2), 315 (4), and 312 (10), 297 (100), 132 (72)
Ultimate analysis
C％ H％ N％
Theoretical value 43.57 4.57 16.94
Measured value 43.39 4.35 16.65
Embodiment 8
1-(6-chloro-3-picolyl)-6-methyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazos [1,2-a] pyridine-5-alcohol (compound 18) synthetic, reaction equation is as follows:
With 2-chloro-5-(2-Nitromethylene-imidazolidine-1-ylmethyl)-pyridine of 0.509g (0.002mol), the anhydrous acetonitrile of 25ml, the rare aldehyde of the methyl-prop of 0.20ml, the AcOH of catalytic amount (can suitably add) places the round-bottomed flask of 50ml.Normal temperature stirs down, has a large amount of solids to separate out (can add the rare aldehyde of an amount of methyl-prop in the reaction process) after about four days.Stopped reaction filters and obtains thick product.It is off-white powder shape solid that recrystallization obtains pure product, productive rate 63%, mp=179.6～181.1 ℃.
1H NMR (500MHz, DMSO): 8.32 (d, J=2.14Hz, 1H, pyridine-H), 7.78 (dd, J
1=2.37Hz, J
2=8.21Hz, 1H, pyridine-H), 7.48 (d, J=8.22Hz, 1H, pyridine-H), 4.80 (m, 1H ,-CHOH), 4.64 (dd, J
1=J
2=15Hz, 2H ,-CH
2-N-), 3.64 (m, 4H, imidazolidine-H), 1.99 (m, 2H ,-CHCH
2-), 1.78 (m, 1H ,-CH
2CH-), 1.05 (d, 3H ,-CH
3);
HR-MS (EI, 1.08e3): M
+.Be C
14H
17N
4O
3Cl, calculated value: 324.0989, measured value: 324.0982, m/z (%)=324 (2), 306 (8), and 294 (10), 291 (100), 244 (43), 126 (70)
Ultimate analysis
C％ H％ N％
Theoretical value 51.78 5.28 17.25
Measured value 51.63 5.11 17.02
Embodiment 9
1-(6-chloro-3-picolyl)-7,8-dimethyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazos [1,2-a] pyridine-5-alcohol (compound 30) synthetic, reaction equation is as follows:
With 2-chloro-5-(2-Nitromethylene-imidazolidine-1-ylmethyl)-pyridine of 0.509g (0.002mol), the anhydrous acetonitrile of 25ml, the 2-methyl-2-butene aldehyde of 0.20ml, the AcOH of catalytic amount (can suitably add) place flask at the bottom of the round bottom of 50ml.Normal temperature stirs down, has a large amount of solids to separate out (can add an amount of 2-methyl-2-butene aldehyde in the reaction process) after about four days.Stopped reaction filters and obtains thick product.It is off-white powder shape solid that recrystallization obtains pure product, productive rate 60%mp=168.6～171.1 ℃.
1HNMR (500MHz, DMSO): 8.34 (d, J=2.14Hz, 1H, pyridine-H), 7.81 (dd, J
1=2.37Hz, J
2=8.21Hz, 1H, pyridine-H), 7.51 (d, J=8.22Hz, 1H, pyridine-H), 4.79 (m, 1H ,-CHOH), 4.61 (dd, J
1=J
2=15Hz, 2H ,-CH
2-N-), 3.67 (m, 4H, imidazolidine-H), 1.96 (m, 1H ,-CHCH-), 1.51 (m, 1H ,-CHCH-), 1.19 (d, 3H ,-CH
3), 1.01 (d, 3H ,-CH
3); HR-MS (EI, 4.33e4): M
+.Be C
15H
19N
4O
3Cl, calculated value: 338.1146, measured value: 338.1140, m/z (%)=338 (2), 320 (7), and 323 (23), 308 (3), 291 (100), 244 (22), 126 (38)
Ultimate analysis
C％ H％ N％
Theoretical value 53.18 5.65 16.54
Measured value 52.95 5.41 17.30
Embodiment 10
1-(6-chloro-3-picolyl)-7-phenyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazos [1,2-a] pyridine-5-alcohol (compound 38) synthetic, reaction equation is as follows:
With 2-chloro-5-(2-Nitromethylene-imidazolidine-1-ylmethyl)-pyridine of 0.509g (0.002mol), the anhydrous acetonitrile of 25ml, the 3-methyl-2-butene aldehyde of 0.20ml, the AcOH of catalytic amount (can suitably add) place flask at the bottom of the round bottom of 50ml.Normal temperature stirs down, has a large amount of solids to separate out (can add an amount of 3-methyl-2-butene aldehyde in the reaction process) after about four days.Stopped reaction filters and obtains thick product.It is off-white powder shape solid that recrystallization obtains pure product, productive rate 40%, mp=229.3-230.1 ℃.
1HNMR (500MHz, DMSO): 8.39 (d, J=2.14Hz, 1H, pyridine-H), 7.87 (dd, J
1=2.37Hz, J
2=8.21Hz, 1H, pyridine-H), 7.32 (d, J=8.2Hz, 1H, pyridine-H), 7.24 (d, J=7.64Hz, 2H, benzene-H), 7.17 (t, 1H, benzene-H), 7.13 (d, J=7.22Hz, 2H, benzene-H), 4.83 (dd, J
1=J
2=15Hz, 2H ,-CH
2-N-), 4.56 (m, 1H ,-CHOH), 4.44 (t, 1H ,-CHCH
2-), 3.66 (m, 4H, imidazolidine-H), 2.33 (m, 2H ,-CH
2CH-), and HR-MS (EI, 5.96e3): M
+.Be C
19H
19N
4O
3Cl, calculated value: 386.1146, measured value: 386.1121, m/z (%)=386 (2), 320 (7), and 340 (7), 210 (10), 208 (21), 126 (100)
Ultimate analysis
C％ H％ N％
Theoretical value 58.99 4.95 14.48
Measured value 58.76 4.87 14.33
Embodiment 11
1-(6-chloro-3-picolyl)-7-methoxyl group-8-nitro-1,2,3,5,6,7-six hydrogen imidazos [1,2-a] pyridine-5-alcohol (compound 42) synthetic:
2-chloro-5-(2-Nitromethylene-imidazolidine-1-ylmethyl)-pyridine with 10.16g (0.04mol), the 100ml anhydrous acetonitrile, the rare aldehyde of 3-methoxy propyl of about 5ml, the AcOH of about 4ml catalytic amount (can suitably add) places the round-bottomed flask of 250ml, 40-45 ℃ of stirring, there is solid to separate out after about one day, stop heating, cooling is filtered and is obtained thick product, it is yellow powder shape solid that recrystallization (MeCN makes solvent) obtains pure product, and productive rate is 70%.
1H NMR (500MHz, DMSO): 8.34 (d, J=2.14Hz, 1H, pyridine-H), 7.79 (dd, J
1=2.37Hz, J
2=8.21Hz, 1H, pyridine-H), 7.50 (d, J=8.22Hz, 1H, pyridine-H), 5.05 (t, 1H ,-CHCH
2-), 4.95 (m, 1H ,-CHOH), 4.84 (dd, J
1=J
2=15Hz, 2H ,-CH
2-N-), 3.97 (s, 3H ,-OCH
3), 3.76 (m, 4H, imidazolidine-H), 2.51 (m, 2H ,-CH
2CH-), and HR-MS (EI, 2.63e3): M
+.Be C
14H
17N
4O
4Cl, calculated value: 340.0938, measured value: 340.0936, m/z (%)=340 (3), 322 (4), and 308 (11), 291 (100), 244 (37), 126 (78)
Ultimate analysis
C％ H％ N％
Theoretical value 49.35 5.03 16.44
Measured value 48.76 4.87 16.33
Embodiment 12
1-(6-chloro-3-picolyl)-6-methoxyl group-8-nitro-1,2,3,5,6,7-six hydrogen imidazos [1,2-a] pyridine-5-alcohol (compound 42) synthetic:
2-chloro-5-(2-Nitromethylene-imidazolidine-1-ylmethyl)-pyridine with 10.16g (0.04mol), the 100ml anhydrous acetonitrile, the rare aldehyde of 2-methoxy propyl of about 5ml, the AcOH of about 4ml catalytic amount (can suitably add) places the round-bottomed flask of 250ml, 40-45 ℃ of stirring, there is solid to separate out after about one day, stop heating, cooling is filtered and is obtained thick product, it is yellow powder shape solid that recrystallization (MeCN makes solvent) obtains pure product, and productive rate is 75%.
1H NMR (500MHz, DMSO): 8.34 (d, J=2.14Hz, 1H, pyridine-H), 7.79 (dd, J
1=2.37Hz, J
2=8.21Hz, 1H, pyridine-H), 7.50 (d, J=8.22Hz, 1H, pyridine-H), 5.05 (t, 1H ,-CHCH
2-), 4.95 (m, 1H ,-CHOH), 4.84 (dd, J
1=J
2=15Hz, 2H ,-CH
2-N-), 3.93 (s, 3H ,-OCH
3), 3.76 (m, 4H, imidazolidine-H), 2.49 (m, 2H ,-CH
2CH-), and HR-MS (EI, 2.63e3): M
+.Be C
14H
17N
4O
4Cl, calculated value: 340.0938, measured value: 340.0936, m/z (%)=340 (3), 322 (4), and 308 (11), 291 (100), 244 (37), 126 (78)
Ultimate analysis
C％ H％ N％
Theoretical value 49.35 5.03 16.44
Measured value 48.76 4.87 16.33
Compound of the present invention can and be eliminated insect widely as control, comprises suction formula worm (Suckinginsects), thorn formula worm (biting insects) and other garden pest, the insect of storage cereal and the sanitary insect pest that causes Health hazard.
The example of insect is as follows:
Coleopteron: sitophilus zea-mais (Sitophilus zeamais), red flour beetle (Tribolium castaneum (Herbst)), potato bug (Henosepilachna vigintioctomaculata), agriotes fussicollis (Agriotesfuscicollis Miwa), square toes green gold tortoise, colorado potato beetles (Monolepta hieroglyphica), the insect of chrysomelid genus (Diabrotica SPP), ponderous borer (Monochamus alternatus Hope), rice root weevil (Echinocnemus squameusBillberg), rice weevil (Echinocnemus bipunctaus), rice water weevil, brown powder is stupid, lepidopterous insects: wave malicious pretty young woman (Lymantria dispar), tent caterpillar Malacosomaneustria testaceaMotschulsky., twill pretty young woman at night, broccoli pretty young woman at night, striped rice borer, Pyrausta nubilalis (Hubern)., meal moth, the lap pretty young woman, chestnut rouleau pretty young woman, a kind of cutworm (Agroti s fucosa), greater wax moth, the dish pretty young woman, the tangerine pretty young woman that dives.Hemipteran: rice green leafhopper Nephotettix cincticeps, Nilaparvata lugen (brown planthopper) Nilaparvata lugens, small brown rice planthopper (Laodelphax striatellus), Bemisia tabaci (Bemisia tabaci), the Kang Shi mealybug, arrowhead scales (Unaspisyanonensis), black peach aphid Myzus persicae, apple aphid, cabbage aphid (Brevicoryne brassicae), radish aphid (Lipaphis erysimi pseudobrassicae), pears class lace bug (Stephanitis nashi Esaki etTakeya), Nazara belongs to insect, bedbug, Trialeurodes vaporariorum Westwood, with the insect (Psylle SPP.) that lice belongs to, orthopteran: Groton bug (B.gormanica Linne), the big Lian of the U.S. (P.Americana Linne), African mole cricket Gryllotalpa africana Palisot et Beauvois. and Asia migratory locusts (L.migratoriamigratoria L).Isoptera insect: (Deucotermes Speratus), Coptotermes formosanus Shtrari (Coptotermesformosanus).Dipteral insect: housefly (Musca do mestica linnac us), Aedes aegypti (Aedesaegypti) is planted fly, culex, Anopheles sinensis (Anopheles sinensis Wiedemann) and three bands are pecked culex, mite class red spider (Tetranychus cinnabarinus).
The compound that the present invention relates to is especially to pierce-suck type, scratching mouthparts insect, as aphid, leafhopper, plant hopper, thrips, aleyrodid, special efficacy is arranged.
These active compounds can be made conventional preparation, solution for example, emulsion, suspensoid, pulvis, granule, foaming agent, paste, granule; Aerosol, particularly soluble solids that Environmental compatibility is good and liquid preparation, as water dispersible granules, water solvent and aqueous emulsion, ultra-low volume preparation etc., with the natural and synthetic material of active substance dipping, the microcapsule in polymer, be used for the dressing compound of seed, with the preparation that uses with combustion unit-piece, sootiness cartridge case for example, sootiness jar and sootiness dish, and cold mist of ULV (Cold mist) and hot mist (Warm mist) preparation.These preparations can be with known method production, for example, with active compound with expand agent and mix, these expand agent is exactly liquid or liquefied gas or the solid diluent or carrier, and can to select tensio-active agent arbitrarily for use be emulsifying agent and/or dispersion agent and/or foam formation agent.For example when using water as the expansion agent, organic solvent also can be used as auxiliary agent.
When making diluent or carrier, be suitable basically with liquid solvent, as arene, dimethylbenzene for example, toluene or alkylnaphthalene; Chlorating fragrance or chlorating fat hydrocarbon, chlorobenzene for example, vinylchlorid or methylene dichloride; Fat hydrocarbon, for example hexanaphthene or paraffin, for example mineral oil fractions; Alcohols, for example ethanol or ethylene glycol and their ether and lipid; Ketone, acetone for example, methylethylketone, methyl iso-butyl ketone (MIBK) or cyclohexanone; Or the polar solvent that is of little use, for example dimethyl formamide and dimethyl sulfoxide (DMSO), and water.
Diluent or carrier with regard to liquefied gas is said, refers to the liquid that will become gas at normal temperatures and pressures, aerosol propellants for example, and as halogenated hydro carbons and butane, propane, nitrogen and carbonic acid gas.
Solid carrier can be used the natural mineral substance in ground, kaolin for example, clay, talcum, quartz, atlapulgite, polynite, or diatomite and ground synthetic mineral substance, for example silicic acid of high dispersing, aluminum oxide and silicate.The solid carrier of using for particle be pulverize with the natural announcement stone of fractionated, calcite for example, marble, float stone, sepiolite and rhombspar, and inorganic and organic meal synthetic particle, with organic materials wood sawdust for example, Exocarpium cocois (Cocos nucifera L), the particle of corn cob and tobacco stems etc.
Non-ionic and anionic emulsifying agent can be used as emulsifying agent and/or foam forms agent.Polyoxyethylene-fatty acid ester for example, polyoxyethylene-Fatty Alcohol(C12-C14 and C12-C18) ethers, for example alkaryl polyoxyethylene glycol ethers, alkyl sulfonates, alkyl sulfuric ester class, aromatic yl sulphonate class and albumin hydrolysate.Dispersion agent comprises, for example xylogen sulfite waste lye and methylcellulose gum.
In preparation, can use tackiness agent, carboxymethyl cellulose and for example, the natural and synthetic polymer of particle or emulsion form, gum arabic for example, the pure and mild polyvinyl acetate of polyvinyl with powder.
Can be with tinting material inorganic dyestuff for example, as ferric oxide, oxidation brill and Zhu of Prussian; Organic dye is as organic dye, as azo dyes or metal titanium cyanine dyes; With use the trace nutrition agent, violent as iron, boron, copper, cobalt, the salt of aluminum and zinc etc.
These preparations contain 0.1-95% active compound by weight usually, preferably contain 0.5-90%.
These active compounds of the present invention can be made in the commodity preparation that a kind of mixture is present in them or from the use formulation of these formulation preparation with other active compounds, these other active compound is a sterilant, bait formulation, sterilant, miticide, nematocides, mycocide, growth control agent etc.Sterilant comprises, phosphoric acid ester for example, amino formate, cinerins, chlorinated hydrocarbons, benzoyl area kind, neires toxin and by the material of microorganisms, as Avrmectin.
In addition, these active compounds of the present invention also can be made in the commodity preparation that a kind of mixture is present in them to become from the use formulation of these formulation preparation with synergistic agent.Synergistic agent is the compound that improves the active compound effect, because active compound itself has activity, also can add synergistic agent.The concentration of making the active compound the use formulation from the commodity preparation can change in wide scope.Use the concentration of the active compound in the formulation can from 0.0000001 to 100% (by active compound weight), be preferably between 0.0001 and 1%.
These compounds are made into suitable available formulation, use with conventional method.
Embodiment 13
The insecticidal activity test of compound of the present invention:
Aphid belongs to homoptera pest, has piercing mouth parts, is a kind of common crop pests.(Aphis craccivora) is tested object with bean aphid, adopts the pickling process test.
Operating process: the accurate various samples of weighing, add N respectively, dinethylformamide is mixed with the 10g/L mother liquor, with the aqueous solution that contains 0.2mL/L Triton X-100 it is diluted to the concentration of 500ug/mL during experiment.Treat aptery one-tenth aphid after stable sucking on the bean sprouts, immersing concentration together with the bean sprouts is 500ug/mL or 100ug/mL, 50,25,12.5, and 6.25ug/mL (tries to achieve LD
50) soup in, take out behind the 5s, inhale with thieving paper and remove unnecessary soup, move in the clean vessel and raise in 23 ℃ of constant temperature.Every concentration is established 3 repetitions, and control group is the aqueous solution that contains 0.2mL/L Triton X-100.Handle after 24 hours, the dead borer population of statistics examination aphid, and calculate mortality ratio (%).The results are shown in Table 1
Plant hopper belongs to homoptera pest, has piercing mouth parts, is a kind of common crop pests.(Nilaparvata lugens) is tested object with brown paddy plant hopper, adopts the spray method test.
Operating process: testing compound accurately is mixed with certain density solution, and makes blank with the clear water processing.Each is handled and repeats 3 glasss (promptly repeating 3 times).With every glass of even spraying 2ml of small-sized hand-operated atomizer.Preceding 6 hours every basins of dispenser connect 10 of planthoppers.3 batches of tests have successively been carried out altogether.Handle after 24 hours, the dead borer population of statistics examination worm, and calculate mortality ratio (%).The results are shown in Table 1 and 2.
Table 1
Table 2
Composition embodiment 1
(a) oily suspension
Any compound 25 weight % among compound a-q in the table 2
Polyoxyethylene sorbitol six oleic acid esters 5 weight %
Senior aliphatics hydrocarbon ils 70 weight %
Each component is ground in sand mill together, up to solid particulate reduce to about below 5 microns till.The thickness suspension of gained can directly use, but also uses after the emulsification in water.
(b) aqeous suspension
Any compound 25 weight % among compound a-q
Hydration attapulgite (hydrate attapulagit) 3 weight %
Calcium lignin sulphonate 10 weight %
SODIUM PHOSPHATE, MONOBASIC 0.5 weight %
Water 61.5 weight %
Each component is ground in ball mill together, up to solid particulate reduce to about below 10 microns till.This aqeous suspension can directly use.
(c) bait formulation
Prepare edible bait by following composition:
Any compound 0.1-10 weight % among compound a-q
Whole meal flour 80 weight %
Molasses 19.9-10 weight %
These components are mixed fully, form the bait shape on demand.The edible bait can be distributed to the place that sanitary insect pest infects, and for example household or industrial site are regional such as kitchen, hospital or shop or open air, to come pest control by oral absorption.
(d) wettability pulvis
Prepare the wettability pulvis by following composition:
Any compound 30 weight % among compound a-q
Sodium dodecylbenzene sulfonate 2 weight %
The 5 weight % of wooden sodium sulfonate
Synthetic florisil 63 weight %
These components are mixed, and in hammer mill, grind to form particle diameter less than 50 microns powder.By dipping or in tap water the mode of oral administration use the plant seed that need use or plant leaf and/or fruit or plant and growing or expect the place that will grow, with pest control.
Embodiment 14: compound 1,3 in the table 1,6 toxicology test
Carried out rat acute per os toxicity test according to GB 15670-1995 State Standard of the People's Republic of China " agriculture chemical registration toxicological experiment method ", the rat acute percutaneous toxicity test, rabbit eye irritant test, rabbit skin irritant test and cavy sensitization test.
The experimental result of above-claimed cpd all shows:
Rat acute per os toxicity test: male, female LD50 is respectively 5000mg/kg, belongs to the micro-virus kind agricultural chemicals.
The rat acute percutaneous toxicity test: male, female LD50 is respectively 5000mg/kg, belongs to the micro-virus kind agricultural chemicals.
In to the rabbit eye irritant test, show as nonirritant.
In to rabbit skin irritant test, show as nonirritant.
The cavy sensitization test does not cause the change of guinea pig skin, belongs to weak sensitizer.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition after having read foregoing of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1, a kind of nitromethylene derivatives, it has following structural formula:
In the formula:
R
1Or/and five yuan of sulphur or hexa-member heterocycle base, or halogenated nitrogenous, oxygen is or/and five yuan of sulphur or hexa-member heterocycle base for nitrogenous, oxygen;
R
2Be H, C
1～C
4Alkyl, C
1～C
4Alkoxyl group or aryl;
R
3Be H, C
1～C
4Alkyl or C
1～C
4Alkoxyl group;
R
4Be H, C
1～C
4Alkyl or C
1～C
4Alkoxyl group or aryl;
R
5Be H, C
1～C
8Saturated or unsaturated alkyl, halogenated C
1～C
8Saturated or unsaturated alkyl ,-CH
2CH
2OCH
2CH
3,-CH
2CH
2OCH
3, C
1～C
8Saturated or unsaturated-oxyl.
2, derivative as claimed in claim 1 is characterized in that, wherein R
1Be a kind of or its chloro thing in tetrahydrofuran base, pyridyl, the thiazolyl.
3, derivative as claimed in claim 2 is characterized in that, wherein R
1For
4, derivative as claimed in claim 1 is characterized in that, wherein R
5Be H or C
1～C
5Saturated or unsaturated alkyl.
5, derivative as claimed in claim 1 is characterized in that, wherein R
2Be H, C
1～C
3Alkyl or C
1～C
3Alkoxyl group; R
3Be H, C
1～C
3Alkyl or C
1～C
3Alkoxyl group; R
4Be H, C
1～C
3Alkyl or C
1～C
3Alkoxyl group.
6, derivative as claimed in claim 1 is characterized in that, wherein R
2Be methyl; R
3Be H; R
4Be H or C
1～C
3Alkyl or C
1～C
3Alkoxyl group; R
5Be H.
7. a pesticide composition is characterized in that, the described formula I derivative of claim 1 or its agricultural that it contains 0.0001wt%-99.9wt% go up suitable salt, and agricultural goes up acceptable diluent or carrier.
8. the method for a pest control is characterized in that, plant seed of using at needs or plant leaf and/or fruit or plant are growing or expecting the place that will grow, uses the described formula I derivative of claim 1 of insecticidal effective dose.
9. the purposes of the described formula I derivative of claim 1 is characterized in that, is used to prepare agricultural chemical insecticide.
10. a method for preparing the described formula I derivative of claim 1 is characterized in that, described method comprises step:
(a) in appropriate solvent, formula II compound and formula III compound are reacted in 60-100 ℃, form formula IV compound;
In the formula, Z=Cl ,-OR ' ,-SR ', wherein R '=C
1-C
3Alkyl (R '=CH preferably
3);
(b) in appropriate solvent, with formula IV compound and formula V compound under the acid catalysis condition in 0-90 ℃ of reaction, form formula (VI) compound:
(c) in appropriate solvent, with formula VI compound and formula VII under the effect of the acid of catalytic amount in 30-70 ℃ of reaction, form formula I compound,
R
5OH (VII)
Wherein, R
1, R
2, R
3, R
4And R
5Definition such as claim 1 described in;
Supplementary condition are, when Z be-OR ' or-SR ' time, any two steps among step (a) and (b), (c) or three steps can merge carries out.
Priority Applications (1)
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